This invention pertains to olefins having a terminally disposed fluorocyclobutyl ring bearing an ionic functionality or a precursor thereto, a process for the production thereof, and polymers, especially ionomers, formed therefrom. The invention further pertains to ionically conductive compositions formed by the combination of a liquid and the ionomer of the invention, and electrochemical devices such as electrodes, sensors, and solid polymer electrolytes comprising those conductive compositions. The polymers of the invention are useful in the formation of films and coatings with high chemical resistance and good physical properties. The ionomers of the invention are useful in electrochemical applications, particularly in lithium batteries. The polymeric compositions of the invention are useful for strong acid catalysis, such as Friedel-Crafts alkylation.
Barrick (U.S. Pat. No. 2,462,347) discloses the 2+2 cycloaddition of fluorinated ethylene whereof at least two of the hydrogens have been replaced by halogens of which at least two must be fluorines, to dienes having two terminally unsaturated bonds of which at least one must be ethylenic to form a fluorocyclobutyl-containing terminal vinyl monomer. Conjugated dienes are preferred. Polymerization, or copolymerization with other unsaturated polymerizable compounds, is carried out in a free-radical initiated process.
Glazkov et al., (Izvest. Akad. Nauk SSSR, Ser. Khim. 10, 2372ff, October 1988) disclose the 2+2 cycloaddition of fluorovinyl ethers to conjugated dienes, particularly 1,3-butadiene and 1,3-pentadiene the reaction occurring at the terminal, rather than the internal, double bond of the pentadiene. Reactants included fluorovinyl ethers of the general formula RfOCFxe2x95x90CF2, wherein Rf is CF2CF(CF3)O(CF2)2SO2F. Synthesis of the cycloadduct was carried out at 120-140xc2x0 C. for 6 hours in an autoclave. At temperatures above 150xc2x0 C. and pressures of 5-10 kbar, the cyclic dimers of the fluorvinyl ethers were formed. Glazkov is silent regarding polymerization.
Roberts et al., (Organic Reactions, Vol. 12, Chapt 1, A. C. Cope, Ed. in Chief, John Wiley and Sons, Inc. New York, 1962) disclose conjugated dienes as highly reactive among unsaturated compounds in cycloaddition reactions with fluoroalkenes; unconjugated dienes are not mentioned. Similarly, Hudlicky (Chemistry of Organic Fluorine Compounds, 2nd ed. P. 450ff, Ellis Horwood PTR Prentice Hall, New York, 1992) dislcose 2+2 cycloaddition reactions between dienes and fluorinated ethylene, but only for conjugated dienes. Hudlicky also discloses the onset of cyclodimerization of reactants at temperature above 200xc2x0 C.
Holler et al., (U.S. Pat. No. 3,481,914) discloses the polymerization of halogen-bearing olefins having a double bond in terminal position and having one of certain halogen-containing groups separated by at least two carbon atoms from said terminal vinyl group, the halogens being attached to primary, secondary, or aromatic carbons, but not to tertiary, allylic or benzylic carbons. Encompassed in the disclosure are terminal olefins having cyclobutyl rings with fluorine-containing substituents on the secondary carbons thereof. Polymerization is carried out by use of Ziegler-type coordination catalysts. Among the catalysts suitable are TiCl3 in combination with Aluminum alkyl.
Coordination polymerization of olefins using metallocene catalysts is disclosed in Welborn et al., U.S. Pat. No. 5,324,800.
Brookhart et al., (WO 9623010A2) discloses a copolymer formed from ethene and a compound represented by the formula H2Cxe2x95x90CH (CH2)aRfR, particularly 1,1,2,2-tetrafluoro-2-[(1,1,2,2,3,3,4,4-octafluoro-9-decenyl)oxy] ethanesulfonyl fluoride, via a catalyzed reaction employing diimine-transition metal complexes. The polymer so-formed comprises a polyethylene backbone having randomly distributed pendant groups of 1,1,2,2-tetrafluoro-2-[(1,1,2,2,3,3,4,4-octafluoro-(mostly)octoxy] ethanesulfonyl fluoride, as well as alkyl branches. Brookhart""s teachings are limited to comonomers having only secondary carbon atoms linking the fluorine-containing group and the olefinic double bond.
It has long been known in the art to form ionically conducting membranes and gels from organic polymers containing ionic pendant groups. Such polymers are known as ionomers. Particularly well-known ionomer membranes in widespread commercial use are Nafion(copyright) Membranes available from E. I. du Pont de Nemours and Company. Nafion(copyright) is formed by copolymerizing tetra-fluoro ethylene (TFE) with perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride), (PSEPVE), as disclosed in U.S. Pat. No. 3,282,875. Also known are copolymers of TFE with perfluoro (3-oxa-4-pentene sulfonyl fluoride), as disclosed in U.S. Pat. No. 4,358,545. The copolymers so formed are convened to the ionomeric form by hydrolysis, typically by exposure to an appropriate aqueous base, as disclosed in U.S. Pat. No. 3,282,875. Lithium, sodium and potassium are all well known in the art as suitable cations for the above cited ionomers.
Doyle et al., (WO 98/20573) disclose a highly fluorinated lithium ion exchange polymer electrolyte membrane (FLIEPEM) exhibiting a conductivity of at least 0.1 mS/cm comprising a highly fluorinated lithium ion exchange polymer membrane (FLIEPM), the polymer having pendant fluoroalkoxy lithium sulfonate groups, and wherein the polymer is either completely or partially cation exchanged; and, at least one aprotic solvent imbibed in said membrane. Electrodes and lithium cells are also disclosed.
In the polymers above-cited, the fluorine atoms provide more than one benefit. The fluorine groups on the carbons proximate to the sulfonyl group in the pendant side chain provide the electronegativity to render the cation sufficiently labile so as to provide high ionic conductivity. Replacement of those fluorine atoms with hydrogen results in a considerable reduction in ionic mobility and consequent loss of conductivity.
The remainder of the fluorine atoms, such as those in the polymer backbone, afford the chemical and thermal stability to the polymer normally associated with fluorinated polymers. This has proven to be of considerable value in such applications as the well-known xe2x80x9cchlor-alkalixe2x80x9d process. However, highly fluorinated polymers also have disadvantages where there is less need for high chemical and thermal stability. The fluorinated monomers are more expensive than their olefin counterparts, require higher processing temperatures, and often require expensive corrosion resistant processing equipment. Furthermore, it is difficult to form solutions and dispersions of fluoropolymers. Additionally, it is difficult to form strong adhesive bonds with fluoropolymers. In materials employed in electrochemical cells, for example, it may be advantageous to have better processibility at some cost to chemical and thermal stability. Thus, there is an incentive to develop ionomers with highly labile cations having reduced fluorine content.
Numerous publications disclose polyethers with either proximal ionic species in the polymer or in combination with ionic salts. Conductivities are in the range of 10xe2x88x925 S/cm and less. Le Nest et al., Polymer Communications 28, 303 (1987) disclose a composition of polyether glycol oligomers joined by phosphate or thiophosphate moieties hydrolyzed to the related lithium ionomer. In combination with propylene carbonate, conductivity in the range of 1-10xc3x9710xe2x88x924 S/cm was realized. A review of the related art is found in Fauteux et al., Electrochimica Acta 40, 2185 (1995).
Benrabah et al., Electrochimica Acta, 40, 2259 (1995) disclose polyethers crosslinked by lithium oxytetrafluorosulfonates and derivatives. No aprotic solvents are incorporated. With the addition of lithium salts conductivity of  less than 10xe2x88x924 S/cm was achieved.
Armand et al., U.S. Pat. No. 5,627,292 disclose copolymers formed from vinyl fluoroethoxy sulfonyl fluorides or cyclic ethers having fluoroethoxy sulfonyl fluoride groups with polyethylene oxide, acrylonitrile, pyridine and other monomers. Lithium sulfonate ionomers are formed. No aprotic solvents are incorporated. Conductivity was  less than 10xe2x88x924 S/cm.
Narang et al., U.S. Pat. No. 5,633,098 disclose polyacrylate copolymers having a functionalized polyolefin backbone and pendant groups containing tetrafluoroethoxy lithium sulfonate groups. The comonomers containing the sulfonate groups are present in molar ratios of 50-100%. Compositions are disclosed comprising the polymer and a solvent mixture consisting of propylene carbonate, ethylene carbonate, and dimethoxyethane ethyl ether. Ionic conductivity of those compositions was in the range of 10xe2x88x924-10xe2x88x923 S/cm.
The present invention provides for a substantially non-fluorinated polyolefin polymer comprising pendant groups comprising the radical of the formula 
wherein R is oxygen or an alkylene or alkylene ether group wherein one or more of the hydrogens may be substituted by halogen, and Rf is a radical of the formula 
wherein Rfxe2x80x2 is a bond or is a fluoroalkylene or fluoroalkylene ether group, Y is F or O, Z is hydrogen or a univalent metal and m=0 or 1 with the proviso that m=0 when Y is F, and m=1 when Y is 0, Rf being ionizable, in character, when m=1.
The present invention further provides for a terminally unsaturated olefin of the formula 
wherein R is oxygen or an alkylene or alkylene ether group wherein one or more of the hydrogens may be substituted by halogen, and Rf is a radical of the formula 
wherein Rfxe2x80x2 is a bond or is a fluoroalkylene or fluoroalkylene ether group, Y is F or O, Z is a univalent metal and m=0 or 1 with the proviso that m=0 when Y is F, and m=1 when Y is O, Rf being ionizable in character when m=1.
Further provided is a process for producing a terminally unsaturated olefin, the process comprising combining in a vessel a diene of the formula
CH2xe2x95x90CHxe2x80x94Rxe2x80x94CHxe2x95x90CH2 xe2x80x83xe2x80x83(IV) 
wherein R is oxygen or an alkylene or alkylene ether group wherein one or more of the hydrogens may be substituted by halogen with up to 50 mol-% of a terminally unsaturated fluoroolefin having the formula 
wherein Rfxe2x80x2 is a bond or is a fluoroalkylene or fluoroalkylene ether group, Y is F or O, Z is a univalent metal and m=0 or 1 with the proviso that m=0 when Y is F, and m=1 when Y is O. Rf being ionizable in character when m=1;
heating to a temperature in the range of 180-600xc2x0 C. for a period of about one second to about 24 hours. The process is preferably followed by cooling and removal of product.
Further provided is a polymerization process the process comprising the copolymerization of an olefin with the terminally unsaturated olefin (III), in the presence of an organometallic coordination catalyst, under polymerization conditions.
Further provided is an ionically conductive composition comprising the polymer having pendant groups (I) wherein, in (II), m=1 and Z is an alkali metal, and a liquid imbibed therewithin.
Further provided is a conductive composition comprising a liquid and the compound described by the formula (III) wherein, in (II), m=1 and Z is an alkali metal.
Further provided is an electrochemical cell comprising a cathode, an anode and a separator, at least one of which comprises the polymer having pendant groups (I) wherein, in (II), m=1 and Z is an alkali metal.
Further provided is an electrochemical cell comprising an anode, a cathode, a separator, and a conductive composition comprising the compound described by the formula (III) wherein, in (II), m=1 and Z is an alkali metal, and a liquid.
Further provided is an electrode comprising an electroactive material and the polymer having pendent groups (I) wherein, in (II), m=1 and Z is an alkali metal.